Neutral primary tertiaralkyl amine salts of tripolyphosphoric acid and phosphoric acid alkyl esters



United States Patent 3,504,055 NEUTRAL PRIMARY TERTIARALKYL AMINE SALTSv OF TRIPOLYPHOSPHORIC ACID AND PHOSPHORIC ACID ALKYL ESTERS Harry J. Andress, Jr., and Julius Capowski, Pitman, N.J., assignors to Mobil Oil Corporation, a corporation of New York No Drawing. Original application Sept. 11, 1964, Ser. No. 395,933. Divided and this application Oct. 6, 1967, Ser. No. 673,309

Int. 'Cl. C07f 9/08; C07c 101 /02; C10] 1 26 US. Cl. 260924 2 Claims ABSTRACT OF THE DISCLOSURE Alkylamine salts, suitable for use as stabilizers for liquid hydrocarbons are provided, containing alkyl substituent groups and being salts of either phosphoric acids, phosphoric acid alkyl esters, boric acid, carbonic acid, aminocarboxylic or hydroxyethyl aminocarboxylic acids.

CROSS-REFERENCE TO RELATED APPLICATIONS Application Ser. No. 395,933, filed Sent. 11, 1964 (parent application).

BACKGROUND OF THE INVENTION Field of the invention This invention, which is a division of our application Ser. No. 395,933, filed Sept. 11, 1964, relates to liquid hydrocarbon fuels. More particularly, the invention relates to liquid hydrocarbon combustion fuels that are stabilized against screen-clogging, filter plugging, sediment formation, icing and corrosion, and the novel additive compounds useful for such purposes.

Description of the prior art As is well known to those skilled in the art, liquid hydrocarbon fuels, particularly hydrocarbon combustion fuels, such as fuel oils, diesel fuels, jet fuels and gasolines, tend to exhibit certain deleterious characteristics either after long periods of storage or under the conditions of operational use. Thus, it has been found that in such fuels, apart from the fact that under storage or operational conditionsthey may exhibit icing, corrosion and sediment formation, a particularly serious problem is encountered in the clogging of screens and plugging of filters. This tendency to clog screens and plug filters results from the caustic treatment of catalytically refined petroleum distillate fuels for the removal of "sulfur-containing materials.

More specifically, this condition occurs when certain polar materials (surface-active additives and trace constituents) in the fuel contacted by the caustic agents, break down and form, as 'part of the product, watersoluble alkali metal compounds. When, subsequently, these fuels contact water such as might be'present in fuel tank bottoms, these alkali metal compounds are leached out of the hydrocarbon phase into the water phase to greater or lesser degrees. There, by replacement of the alkali metals, corresponding compounds of dissolved metals having normal valences greater than one (for, e.g., calcium, magnesium, zinc, copper, iron,v aluminum, barium or lead) may be formed. Because of their surface activity, and reduced water and product solubility, these compounds may cause emulsification and gel formation particularly in the hydrocarbon layer, as well as in the water layer, with consequent serious detrimental eifects on the clogging of screens and the plugging of filters. Heretofore, certain organic amine monophosphates have been suggested as antiicers, carburetor detergents and antirust agents; however, these additives have, nevertheless,

Patented Mar. 31, 1970 SUMMARY OF THE INVENTION In accordance with the present invention, as more fully hereinafter described, it has been found that the above objects can be attained by the addition of small amounts of additive compositions having the formula:

R R and R are selected from the group consisting of hydrogen and alkyl groups having from 1 to about 22 carbon atoms, and preferably, from about 8 to about 18 carbon atoms, X is an acid radical selected from the group consisting of (a) phosphoric acids having from 2 to 8 phosphorus atoms per molecule, (b) phosphoric acid alkyl esters having from 2 to 8 phosphorus atoms per molecule and containing from 1 to 4 alkyl groups having from 1 to 22 carbon atoms per alkyl group, (0) boric acid, (d) carbonic acid, (e) aminopolycarboxylic acids and hydroxyethyl aminocarboxylic acids, in which the amine nitrogen atom is separated from the carboxylic carbon atom by a methylene or ethylene linkage and in which when more than one nitrogen atom is present they are separated from each other by ethylene or propylene linkages, and n is a whole number from 1 to 5, the maximum value of n being limited by the number of replaceable hydrogen atoms in the acid molecule of which X is an acid radical.

More specifically, with respect to the aforementioned substituents for the acid radical X, phosphoric acids of the type indicated under (a) may include pyrophosphoric acid (diphosphoric acid), triphosphoric acid, hexaphosphoric acid and polyphosphoric acid. Aminopolycarboxylic acids of the type indicated under (e) may include ethylenediamine tetraacetic acid, nitrilotriacetic acid, diaminocyclohexane-N,N'-tetraacetic acid, and diethylenetriamine pentaacetic acid. Hydroxyethyl aminocarboxylic acids indicated under (e) may include N-hydroxyethyl ethylenediamine triacetic acid and dihydroxyethyl glycine.

As will become hereinafter apparent, these additive compositions are particularly effective not only as stabilizers against icing, corrosion and sediment formation, but also as antiscreen clogging and filter plugging agents in liquid hydrocarbon fuels.

These beneficial effects result from the fact that in the previously described replacement of the alkali metals, those metals having valences greater than one are tied up and rendered unavailable. As a result of such action, the aforementioned detrimental eifects are prevented from occurring.

The alkylamine salt additives are, in general, prepared by reacting one equivalent of the selected amine with one equivalent of the selected acid, in accordance with the above-described general formula, preferably at elevated temperature, for example, from about 50 C. to about 120 C.

The aforementioned alkylamine salt additives may be used to improve liquid hydrocarbon fuels, generally. Of particular significance is the use of these additives to improve liquid hydrocarbon fuels comprising petroleum' distillates, which are hydrocarbon fractions, having an initial boiling point of at least about F. and anend boiling Such fuels are generally referred to as distillate'fuel oils. It will be understood, however, that this terminology is not restricted to straight-run distillate fractions. The distillate fuel oils may comprise straight-run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillate fuel oils, napthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well known commercial methods, such as, acid or caustic treatment, hydrogenation, solvent refining, clay treatment and the like.

The distillate fuel oils are characterized by their relatively low viscosities, pour points and the like. The principal properties which characterizes the contemplated liquid hydrocarbon fuels of the present invention, however, is their distillation range. As previously indicated, this range will lie between about 90 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range, falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.

Particularly contemplated among the aforementioned liquid hydrocarbon fuel oils are gasolines, Nos. 1, 2 and 3 fuel oils used in heating, diesel fuel oils, and the jet combustion fuels. The gasolines generally boil within the range from about 90 F. to about 450 The domestic fuel oils generally conform to the specifications set forth in ASTM Specifications D396-62T. Specifications for diesel fuels are defined in ASTM Specifications D975 60T. Typical jet fuels are defined in Military Specifications MIL-F-5624B.

The amount of the aforementioned alkylamine salt additive contemplated for use herein which is added to the liquid hydrocarbon fuel will depend, of course, upon the intended and the particular additives selected, inasmuch as these additives may necessitate being used in greater concentrations than others to be effective. In most cases, in which it is desired to obtain the aforementioned beneficial results in the liquid hydrocarbon fuels, viz. prevention of clogging of screens and plugging of filters, in addition to stabilization against sediment formation, icing and corrosion, additive concentrations varying from about 1 to about 200 pounds per thousand barrels of the fuel will be employed. Preferably, it will vary from about 5 to about 25 pounds per 100 barrels of fuel. If so desired, the aforementioned liquid hydrocarbon fuel compositions of the present invention can contain other additives for the purpose of achieving other results. Thus, for example, there may be present foam inhibitors, ignition and burning quality improves, and others. Examples of such additives are silicones, dinitropropane, amyl nitrate, metal sulfonates, and the like.

DESCRIPTION OF SPECIFIC EMBODIMENTS The following examples and comparative data are intended to illustrate the novel additive compositions of the present invention and also to demonstrate their effectiveness in improving the properties of liquid hydrocarbon fuels. -It will be understood, of course, that it is not intended the invention to be limited to the particular compositions shown or to the operations or manipulations involved. Various other additive compositions, and other fuels, can be utilized as those skilled in the art will readily appreciate.

In carrying out the comparative experimentation, previously referred to, laboratory bench tests were made in which 40 m1. of an average commercially available gasoline blend, (comprising, by volume, 40% catalytically cracked, 40% reformate and 20% alkylate components), was treated with ml. of 0.8 N NaOH (as a sulfur compound, particularly mercaptan, removing agent), 6 ml. of distilled water and 20 ml. of 13 g./l., of ZnCl solution (a component providing zinc ions which are often present in the field in tank water bottoms as a result of "chemical actions on "galvanized metal surfaces) ina'-100 ml. of mixing graduate. This mixture was given fifteen uniform, moderate, shakings and allowed to settle for one one minute. The mixture was then examined for indications of colloidal states. The following table indicates the results obtained in such examinations. With regard to this table, it should be noted that the laboratry tests simulate the most severe conditions of commercial use that would normally be expected to result in emulsion and gel formation, which would otherwise cause handling difficulties in product distribution systems and in vehicle fuel lines, with particular emphasis residing in encountering screenclogging and filter plugging. As will be seen from the table, under such conditions the additives of the present invention reduced, to a very significant degree, the tendency of the uninhibited gasoline and uninhibited gasoline containing an alkylamine monophosphate (as a typical antiicer, antirust and carburetor detergent multifunctional additive) to form emulsions.

The additives of the following table were prepared as follows:

EXAMPLE I Preparation of Primene 81R salt of tripolyphosphoric acid A mixture comprising: 74 grams (0.2 mol) sodium tripolyphosphate (Na P O 200 grams water and 36.7 grams hydrochloric acid grams of 36.7% hydrochloric acid solution) was stirred for a period of one hour at 60 C. and then heated to C. to form the free tripolyphosphoric acid. To this mixture were then added 200 grams (1 mol) of Primene 81R (a commercially available mixture of branched chain amines of from about 12 to about 15 carbon atom chain lengths having the primary amine group directly attached to a tertiary carbon atom) and 100 grams of benzene. The resulting mixture was then heated to 100 C. and maintained at this temperature for a period of one hour. The resulting water layer was then removed from the mixture by the use of a separatory funnel. The remaining mixture was then topped at 180 C. under reduced pressure and filtered to yield the desired product of the Primene 81R salt of tripolyphosphoric acid.

EXAMPLE II Preparation of tetra Primene 81R salt of ethylene'diamine tetraacetic acid A mixture comprising: 200 grams (1 mol) Primene 81R, 73 grams (0.25 mol) ethylenediamine tetraacetic acid and 273 grams of xylene as a diluent was stirred for a period of about two hours at a temperature from about C. to about C. to form the tetra Primene 81R salt of ethylenediamine tetraacetic acid, diluted with 50% xylene.

Another group of useful additives of the aforementioned type are the Primene 81R salts of alkyl phosphoric acid esters having from 2 to 8 phosphorus atoms, an acid number from about 200 to about 750 and from 1 to 12 carbon atoms per alkyl group. Examples III and IV illustrate two typical types of this group.

EXAMPLE III Preparation of Primene 81R salt of Phosphonol H A mixture comprising: 100 grams of mixed alkyl polyphosphoric acid esters (commercially available under the tradename Phosphonol H, falling within the descriptive properties indicated above and having an acid number of 302, was stirred for a period of about one hour at a temperature of 100 C. with 108 grams of Primene 81R to form the Primene 81R salt of Phosphonol H.

EXAMPLE IV Preparation of Primene 81R salt of Strodex P-100 A mixture comprising 110 grams of mixed alkyl polyphosphoric acid esters (commercially available under the tradename Strodex P-l00, falling within the descriptive properties indicated above and having an acid number of 240, was stirred for a period of about two hours at a temperature of 150 C. with 94 grams of Pn'mene 81R phoric acid wherein said acid corresponds to the acid form of Na P O the primary alkyl amine is a mixture of branched chain amines having from about 8 to 18 carbon atoms, the primary amine group is directly atto form the Primene 81R salt of Strodex P100. 5 tached to a tertiary carbon atom.

TABLE Demulsification Test Concen- Gasoline tration, layer, lbs/1,000 percent Water layer, bbls. emulsified observations (1) Blank gasoline l 40 Cloudy with heavy precipitate. (2) Blank gasoline a commercial alkylamine 100 80 Cloudy with moderate precipitate.

monophosphate. (3) Bianx gasoline Primene 81 R salt of tri- 100 10 Cloudy with slight precipitate.

polyphosphoric acid. (4) Blank gasoline tetra Primene 81 R salt of mu 0 Cloudy with moderate precipitate.

ethylenediamine tetraacetic acid. (5) Blank gasoline Primene 81 R salt of 100 Cloudy with slight precipitate.

Phosphonol H. (6) Blank gasoline Primene 81 R salt of 100 0 Cloudy with moderate precipitate Strodex P-100.

A commercial type eatalytically eracked/reiormate/alkylate gasoline blend containing 5 lb./1,000 barrel 2,6 ditertiary butyl paracresol; 1 lb./1,000 barrels N ,N-d1sal1cylidene-1,2-propanediamine; and 3 cc. tetraethyls lead/gal. 7

While the present invention has been described with preferred embodiments, it should be understood that modifications and variations thereof may be resorted to without departing from the spirit of the invention as Will be obvious to those skilled in the art.

We claim:

1. The neutral primary alkyl amine salt of an alkyl phosphoric acid ester having from 2 to 8 phosphorus atoms, an acid number from about 200 to about 750 and from 1 to 12 carbon atoms per alkyl group, wherein the primary alkyl amine is a mixture of branched chain amines having from about 8 to 18 carbon atoms, having the primary amine group directly attached to a tertiary carbon atom.

2. The neutral primary alkyl amine salt of tripolyphos- References Cited UNITED STATES PATENTS CHARLES B. PARKER, Primary Examiner A. H. SUTTO, Asistant Examiner US. Cl. X.R.

Patent No. 3,50%055 Dated March 3 97 Inventor(s) Harry J. Andreas, Jr. and Julius Capowski It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 71, for "more" read --h1gher-- Column 3, line 7 for "13 3/1" read --13.6 g/l-- Column 4, line 2, "of" should be omitted Column 4, lines 3 and 4, for "one one minute" read --one minute-- SIGNED A SEALED JUL 2 8 70 M3Lfi$ mt: smmm mm m. mmhqh mm x. ng Manual- 01' PM? 

